Heat-resistant regenerated polypropylene material and preparation method thereof
阅读说明：本技术 耐热型再生聚丙烯材料及其制备方法 (Heat-resistant regenerated polypropylene material and preparation method thereof ) 是由 �谷洋 马令庆 于 2021-01-04 设计创作，主要内容包括：本发明提出一种耐热型再生聚丙烯材料及其制备方法,属于再生聚丙烯材料领域,能够解决现有聚丙烯材料存在易降解、各项性能降低、无法实现循环再利用等的技术问题。该耐热型再生聚丙烯材料配方,以重量份数计,包括：再生聚丙烯80-90份、自由基引发剂0.01-1.0份、自由基控制剂0.01-1.0份、扩链剂0.5-2.0份、增韧剂1-10份、增强剂1-10份、加工助剂0.5-2.0份。本发明能够应用于冰箱蒸发皿及其他零部件方面。(The invention provides a heat-resistant regenerated polypropylene material and a preparation method thereof, belongs to the field of regenerated polypropylene materials, and can solve the technical problems that the existing polypropylene material is easy to degrade, various performances are reduced, recycling cannot be realized, and the like. The heat-resistant regenerated polypropylene material comprises the following components in parts by weight: 80-90 parts of regenerated polypropylene, 0.01-1.0 part of free radical initiator, 0.01-1.0 part of free radical control agent, 0.5-2.0 parts of chain extender, 1-10 parts of flexibilizer, 1-10 parts of reinforcing agent and 0.5-2.0 parts of processing aid. The invention can be applied to the aspects of the evaporating dish of the refrigerator and other parts.)
1. The heat-resistant regenerated polypropylene material is characterized by comprising the following components in parts by weight: 80-90 parts of regenerated polypropylene, 0.01-1.0 part of free radical initiator, 0.01-1.0 part of free radical control agent, 0.5-2.0 parts of chain extender, 1-10 parts of flexibilizer, 1-10 parts of reinforcing agent and 0.5-2.0 parts of processing aid.
2. The heat-resistant recycled polypropylene material as claimed in claim 1, wherein the recycled polypropylene is selected from polypropylene parts and components crushed and recycled materials of any one or more of refrigerator drawers, air duct cover plates, evaporating dishes, washing machine tubings, ton bags and television shells.
3. A heat-resistant reclaimed polypropylene material according to claim 1, wherein the radical initiator is at least one selected from the group consisting of t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-amyl peroxyacetate, t-butyl peroxyisononanoate, t-butyl peroxyacetate, t-butyl peroxymaleate, t-butyl peroxybenzoate, dicumyl peroxide, t-butylperoxycumene and di-t-butyl peroxide, and is preferably at least one selected from the group consisting of t-butyl peroxybenzoate, dicumyl peroxide and t-butylperoxycumene.
4. The heat-resistant recycled polypropylene material as claimed in claim 1, wherein the radical controller is a dithioester compound or a trithioester compound, and has the following structural formula:
in the above formula: z is selected from aryl or alkylthio, R1Selected from benzyl, cyanoisopropyl or carboxyisopropyl.
5. The heat-resistant reclaimed polypropylene material according to claim 4, wherein the radical-controlling agent is at least one selected from the group consisting of 2-cyano-2-propylbenzodithiol, 2- (dodecyltrithiocarbonate) -2-methylpropionic acid, polyethylene glycol-4-cyano-4- (phenylcarbonylthiothiothio) valerate, 4-cyano-4- [ (dodecylsulfanylthiocarbonyl) sulfanyl ] pentanol and benzyl benzodithiocarbamate, and is preferably at least one selected from the group consisting of polyethylene glycol-4-cyano-4- (phenylcarbonylthiothiothiothio) valerate and 4-cyano-4- [ (dodecylsulfanylthiocarbonyl) sulfanyl ] pentanol.
6. The heat-resistant recycled polypropylene material according to claim 1, wherein the chain extender is at least one selected from the group consisting of 1, 6-hexanediol ethoxylate diacrylate, tetraethylene glycol diacrylate, 1, 4-butanediol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, pentaerythritol diacrylate and polyethylene glycol diacrylate, and preferably at least one selected from the group consisting of 1, 6-hexanediol ethoxylate diacrylate, tetraethylene glycol diacrylate and polyethylene glycol diacrylate.
7. The heat-resistant recycled polypropylene material as claimed in claim 1, wherein the toughening agent is at least one selected from polyolefin elastomer grafted maleic anhydride copolymer and ethylene propylene diene monomer grafted maleic anhydride copolymer; the reinforcing agent is selected from at least one of calcium carbonate, barium sulfate and talcum powder; the processing aid is at least one of ethylene bis stearamide, dipentaerythritol, silicone oil, low molecular weight polyethylene and solid paraffin.
8. The method for preparing the heat-resistant recycled polypropylene material according to any one of claims 1 to 7, comprising the steps of:
drying the regenerated polypropylene for 2-3h at the temperature of 60-80 ℃ to obtain dried regenerated polypropylene;
adding the dried regenerated polypropylene, the free radical initiator, the free radical control agent, the chain extender, the flexibilizer, the reinforcing agent and the processing aid into a high-speed mixer according to the mass part ratio, and stirring and mixing for 10-30min to prepare a mixture A;
and adding the mixture A into a double-screw extruder, and performing blending, extrusion, cooling and granulation treatment to finally obtain the heat-resistant regenerated polypropylene material.
9. The production method according to claim 8, wherein the temperature setting conditions of the twin-screw extruder are: the pre-melting temperature zone is 140-.
10. The preparation method as claimed in claim 9, wherein the screw rotation speed of the twin-screw extruder is 300-400r/min, and the reaction time is 1-10 min.
Technical Field
The invention relates to a regenerated polypropylene material, in particular to a heat-resistant regenerated polypropylene material and a preparation method thereof.
Background
Polypropylene (PP), which is a polymer obtained by addition polymerization of propylene, has the advantages of low density, low cost, high strength, heat resistance, acid and alkali resistance, and is widely used in the fields of chemical industry, agriculture, automobiles, home appliances, and home appliances, but since this material cannot be biodegraded and will exist in nature for a long time after being discarded, causing environmental pollution, the "white pollution" caused by "white plastics" such as polypropylene is attracting more and more attention, and is a subject to be solved urgently.
14 months 5 in 2020, the State development and reform Commission, Ministry of industry and informatization, Ministry of finance, Ministry of ecological environment, Ministry of housing, urban and rural construction, Ministry of commerce and market supervision, jointly issues an implementation scheme for improving the recovery and treatment system of waste and old household appliances and promoting the update and consumption of household appliances so as to promote the update and consumption of household appliances, and simultaneously, provides new requirements for the industry of household appliances, namely how to realize the recycling of household electrical appliance materials, in the processing and using process of the current polypropylene materials, because the functions of pyrolysis, oxidation, illumination and the like can be seriously degraded and the molecular weight is obviously reduced, the properties of the regenerated polypropylene are deteriorated and the use requirements of daily life products can not be met, therefore, how to improve the heat resistance, strength and other properties of the polypropylene material by optimizing the polypropylene processing technology and finally realize the recycling of the polypropylene material is an important way to solve the above problems.
Disclosure of Invention
The invention provides a heat-resistant regenerated polypropylene material which is high in strength, excellent in heat resistance and capable of realizing recycling, aiming at the technical problems that the existing polypropylene material is easy to degrade, various performances are reduced, recycling cannot be realized and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
the heat-resistant regenerated polypropylene material comprises the following components in parts by weight: 80-90 parts of regenerated polypropylene, 0.01-1.0 part of free radical initiator, 0.01-1.0 part of free radical control agent, 0.5-2.0 parts of chain extender, 1-10 parts of flexibilizer, 1-10 parts of reinforcing agent and 0.5-2.0 parts of processing aid.
Preferably, the recycled polypropylene is selected from one or more polypropylene parts crushed and recycled in a drawer of a refrigerator, an air duct cover plate, an evaporation pan, a barrel material of a washing machine, a ton bag and a television shell.
Preferably, the radical initiator is selected from at least one of t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-amyl peroxyacetate, t-butyl peroxyisononanoate, t-butyl peroxyacetate, t-butyl peroxymaleate, t-butyl peroxybenzoate, dicumyl peroxide, t-butyl cumyl peroxide and di-t-butyl peroxide, and is preferably at least one of t-butyl peroxybenzoate, dicumyl peroxide and t-butyl cumyl peroxide.
Preferably, the free radical control agent is a disulfide ester compound or a trithioester compound, and the structural formula of the compound is as follows:
in the above formula: z is selected from aryl or alkylthio, R1Selected from benzyl, cyanoisopropyl or carboxyisopropyl.
Preferably, the radical control agent is selected from at least one of 2-cyano-2-propylbenzodithio, 2- (dodecyltrithiocarbonate) -2-methylpropionic acid, polyethylene glycol-4-cyano-4- (phenylcarbonylthiothiothio) valerate, 4-cyano-4- [ (dodecylsulfanylthiocarbonyl) sulfanyl ] pentanol and benzyl benzodithiocarbamate, preferably at least one of polyethylene glycol-4-cyano-4- (phenylcarbonylthiothiothio) valerate and 4-cyano-4- [ (dodecylsulfanylthiocarbonyl) sulfanyl ] pentanol.
Preferably, the chain extender is selected from at least one of 1, 6-hexanediol ethoxylate diacrylate, tetraethylene glycol diacrylate, 1, 4-butanediol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, pentaerythritol diacrylate and polyethylene glycol diacrylate, and preferably at least one of 1, 6-hexanediol ethoxylate diacrylate, tetraethylene glycol diacrylate and polyethylene glycol diacrylate.
Preferably, the toughening agent is selected from at least one of polyolefin elastomer grafted maleic anhydride copolymer and ethylene propylene diene monomer grafted maleic anhydride copolymer; the reinforcing agent is selected from at least one of calcium carbonate, barium sulfate and talcum powder; the processing aid is at least one of ethylene bis stearamide, dipentaerythritol, silicone oil, low molecular weight polyethylene and solid paraffin.
The invention also provides a preparation method of the heat-resistant regenerated polypropylene material by using any one of the preferable technical schemes, which comprises the following steps:
drying the regenerated polypropylene for 2-3h at the temperature of 60-80 ℃ to obtain dried regenerated polypropylene;
adding the dried regenerated polypropylene, the free radical initiator, the free radical control agent, the chain extender, the flexibilizer, the reinforcing agent and the processing aid into a high-speed mixer according to the mass part ratio, and stirring and mixing for 10-30min to prepare a mixture A;
and adding the mixture A into a double-screw extruder, and performing blending, extrusion, cooling and granulation treatment to finally obtain the heat-resistant regenerated polypropylene material.
Preferably, the temperature setting conditions of the twin-screw extruder are as follows: the pre-melting temperature zone is 140-.
Preferably, the screw rotating speed of the double-screw extruder is 300-400r/min, and the reaction time is 1-10 min.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the invention provides a heat-resistant regenerated polypropylene material, which mainly aims at the problems that the existing regenerated polypropylene material has poor mechanical property and cannot meet the application requirement of a finished piece when being directly used, and the like, and the heat-resistant regenerated polypropylene material realizes the generation of in-situ block/graft polypropylene by adding a free radical initiator and a free radical control agent in the preparation process and by means of the controllability of reversible addition-fragmentation chain transfer polymerization, can improve the mechanical property and the heat resistance of a regenerated polypropylene matrix, and can further strengthen the toughened regenerated polypropylene by combining a toughening agent and a reinforcing agent on the basis so as to meet the use requirements of parts such as an evaporating dish of a refrigerator and the like;
2. the heat-resistant recycled polypropylene material provided by the invention has the tensile strength of more than or equal to 30MPa, the elongation at break of up to 66 percent and the IZOD impact strength of up to 20.6KJ/m2The Vicat softening temperature is more than or equal to 90 ℃.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a heat-resistant regenerated polypropylene material which comprises the following components in parts by weight: 80-90 parts of regenerated polypropylene, 0.01-1.0 part of free radical initiator, 0.01-1.0 part of free radical control agent, 0.5-2.0 parts of chain extender, 1-10 parts of flexibilizer, 1-10 parts of reinforcing agent and 0.5-2.0 parts of processing aid.
In a preferred embodiment, the recycled polypropylene is selected from polypropylene parts and parts crushed and returned from any one or more of a refrigerator drawer, an air duct cover plate, an evaporation pan, a washing machine barrel material, a ton bag and a television shell.
In a preferred embodiment, the free radical initiator is selected from at least one of tert-butyl peroxy-2-ethylhexanoate (TBPEH), tert-butyl peroxyisobutyrate (TBPI), tert-amyl peroxyacetate (TAPA), tert-butyl peroxyisononanoate (TBPMH), tert-butyl peroxyacetate (TBPA), tert-butyl peroxymaleate (TBPMA), tert-butyl peroxybenzoate (TBPB), dicumyl peroxide (DCP), tert-butyl cumyl peroxide (TBCP), di-tert-butyl peroxide (DTBP), preferably tert-butyl peroxybenzoate, dicumyl peroxide and tert-butyl cumyl peroxide.
In a preferred embodiment, the radical control agent is a disulfide compound or a trithioester compound, and the structural formula is as follows:
in the above formula: z is selected from aryl or alkylthio, R1Selected from benzyl, cyanoisopropyl or carboxyisopropyl.
In the above preferred embodiment, Z is a group capable of activating the addition of a C ═ S double bond to a free radical, and the specific type is not limited to an aromatic group or an alkyl group, and other groups capable of performing the above functions are also within the scope of the present invention, and R is a group capable of activating the addition of a C ═ S double bond to a free radical1It is a group which can easily form active free radical, and its specific type is not limited to cumyl or cyanocumyl, but other groups which can play the role mentioned above are also within the protection scope of the present invention.
In a preferred embodiment, the radical control agent is selected from at least one of 2-cyano-2-propylbenzodithiol (CTA-1), 2- (dodecyltrithiocarbonate) -2-methylpropionic acid (CTA-2), polyethylene glycol-4-cyano-4- (phenylcarbonylthiothiothio) valerate (CTA-3), 4-cyano-4- [ (dodecylsulfanylthiocarbonyl) sulfanyl ] pentanol (CTA-4), benzyl benzodithiocarbamate (CTA-5), preferably at least one of polyethylene glycol-4-cyano-4- (phenylcarbonylthiothiothio) valerate and 4-cyano-4- [ (dodecylsulfanylthiocarbonyl) sulfanyl ] pentanol.
In the preferred embodiment described above, the reason why the present invention chooses to add the radical control agent is that: the traditional free radical polymerization is often difficult to control due to the characteristics of slow chain initiation rate, fast chain growth rate, easy occurrence of irreversible chain transfer and the like, such as: the phenomenon of automatic acceleration commonly occurs in the polymerization process, so that gelation and even implosion are easily caused; the molecular weight distribution of the polymerization product is wide, and the tensile strength, heat resistance and other properties of the polymer can be reduced to a certain extent by the product with small molecular weight. Therefore, the concentration of the free radicals is adjusted to a relatively stable level through the free radical control agent, so that the polymerization process has a smooth chain growth rate, and certain controllability is given to the polymerization process. One of the more successful methods is reversible addition-fragmentation chain transfer (RAFT) polymerization, which is based on the principle that a Chain Transfer Agent (CTA), namely a disulfide ester compound or a trithioester compound, has a high chain transfer constant and is generally much higher than the chain growth rate of a growing active radical, and the growing active radical and the chain transfer agent perform a rapid reversible chain transfer reaction to maintain the concentration of the growing radical at a relatively constant level, so that the radical polymerization has the characteristics of living polymerization and realizes controllable radical polymerization.
In a preferred embodiment, the chain extender is selected from at least one of 1, 6-hexanediol ethoxylate diacrylate, tetraethylene glycol diacrylate, 1, 4-butanediol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, pentaerythritol diacrylate and polyethylene glycol diacrylate, preferably at least one of 1, 6-hexanediol ethoxylate diacrylate, tetraethylene glycol diacrylate and polyethylene glycol diacrylate.
In the above preferred embodiment, the chain extender is a compound with an acrylate terminal double bond, wherein the double bond activity of the acrylate olefin is proper, the acrylate double bond is also beneficial to free radical polymerization, the polymer rate is moderate, the polymerization reaction is convenient to control, the generation of block and grafted polypropylene is promoted, and the gel reaction is prevented.
In a preferred embodiment, the toughening agent is selected from at least one of polyolefin elastomer grafted maleic anhydride copolymer and ethylene propylene diene monomer grafted maleic anhydride copolymer; the reinforcing agent is selected from at least one of calcium carbonate, barium sulfate and talcum powder; the processing aid is at least one of ethylene bis stearamide, dipentaerythritol, silicone oil, low molecular weight polyethylene and solid paraffin.
In the above preferred embodiment, the chain extender is acrylate, and in order to increase the compatibility between the acrylate and the polypropylene, the polyolefin copolymer of maleic anhydride is selected. The reason is that the polyolefin copolymer grafted with maleic anhydride is beneficial to increasing the compatibility between polypropylene and polar components of chain extender segments on one hand; on the other hand, the polyolefin elastomer and the ethylene propylene diene monomer are nonpolar polymers, have good compatibility with polyolefins such as polypropylene and the like, are excellent toughening agents for the polyolefin, can further improve the toughness of the polypropylene, improve the impact resistance of the regenerated polypropylene material, and enable a workpiece to have excellent anti-falling performance and the like.
In addition, the reinforcing agent selected by the invention is rigid nano particles, such as one or more of calcium carbonate, barium sulfate, talcum powder and the like. Usually, pure polypropylene is soft and has insufficient strength, and a part is easy to deform under stress. Therefore, by adding the rigid particles, the rigidity and the strength of the polypropylene are enhanced, and the dimensional stability of the workpiece is improved; the processing aid selected by the invention is a lubricant, the polymerization reaction is controlled to proceed towards the direction of the block/graft polypropylene by RAFT polymerization, the viscosity of the molten mass will be greatly increased along with the rapid increase of the molecular weight, and the problem of uneven polymerization reaction caused by the processing difficulty is prevented. Therefore, the lubricant is added to promote the flow of the melt, and good processing fluidity promotes the polymerization reaction to proceed uniformly and smoothly.
The invention also provides a preparation method of the heat-resistant recycled polypropylene material by using any one of the preferred embodiments, which comprises the following steps:
s1, drying the regenerated polypropylene at the temperature of 60-80 ℃ for 2-3h to obtain dried regenerated polypropylene;
in the step S1, the polypropylene drying temperature can be selected from 60, 70, 80 ℃ or any value within the above range, and the invention is within the protection scope.
S2, adding the dried regenerated polypropylene, the free radical initiator, the free radical control agent, the chain extender, the toughening agent, the reinforcing agent and the processing aid into a high-speed mixer according to the mass part ratio, and stirring and mixing for 10-30min to obtain a mixture A;
s3, adding the mixture A into a double-screw extruder, and performing blending, extrusion, cooling and granulation treatment to finally obtain the heat-resistant regenerated polypropylene material.
In a preferred embodiment, the temperature setting conditions of the twin-screw extruder are: the pre-melting temperature zone is 140-.
In the above preferred embodiment, the temperature of the pre-melting temperature zone may be 140, 150, 160 ℃ or any value within the above range, the temperature of the first zone may be 170, 180, 190 ℃ or any value within the above range may be within the protection range of the present invention, the temperature of the second zone may be 190, 200, 210 or any value within the above range may be within the protection range of the present invention, the temperature of the third zone may be 210, 220, 230 ℃ or any value within the above range may be within the protection range of the present invention, the temperature of the fourth zone may be 200, 210, 220 ℃ or any value within the above range may be within the protection range of the present invention, and the temperature of the discharge port may be 190, 200 ℃ or any value within the above range may be within the protection range of the present invention.
In a preferred embodiment, the screw rotating speed of the double-screw extruder is 300-400r/min, and the reaction time is 1-10 min.
In order to more clearly and specifically describe the heat-resistant recycled polypropylene material and the preparation method thereof provided by the embodiments of the present invention, the following description will be made with reference to specific examples.
Comparative example 1
The comparative example provides a formula of a regenerated polypropylene material and a preparation method thereof, and the specific contents are as follows:
the raw material formula comprises the following raw materials in parts by weight:
85 parts of regenerated polypropylene, 8 parts of a toughening agent (ethylene propylene diene monomer grafted maleic anhydride copolymer), 6 parts of a reinforcing agent (calcium carbonate) and 0.4 part of a processing aid (ethylene bis stearamide);
the preparation method comprises the following steps:
(1) drying the regenerated polypropylene at the temperature of 70 ℃ for 3 h;
(2) according to the mass ratio, adding the weighed regenerated polypropylene, the ethylene propylene diene monomer grafted maleic anhydride copolymer, the calcium carbonate and the ethylene bis stearamide into a high-speed mixer, and stirring and mixing for 20min to obtain a mixture A;
(3) adding the mixture A into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the pre-melting temperature zone is 155 ℃, the first zone is 180 ℃, the second zone is 200 ℃, the third zone is 210 ℃, the fourth zone is 200 ℃, and the discharge port temperature zone is 190 ℃; the rotating speed of the screw is 300r/min, and the regenerated polypropylene material is finally prepared after melt blending, extrusion, cooling and granulation.
Comparative example 2
The comparative example provides a formula of a regenerated polypropylene material and a preparation method thereof, and the specific contents are as follows:
the raw material formula comprises the following raw materials in parts by weight:
85 parts of regenerated polypropylene, 0.01 part of a free radical initiator (dicumyl peroxide), 0.1 part of a free radical control agent (polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate), 0.5 part of a chain extender (polyethylene glycol diacrylate) and 0.4 part of a processing aid (ethylene bis stearamide);
the preparation method comprises the following steps:
(1) drying the regenerated polypropylene at the temperature of 70 ℃ for 3 h;
(2) according to the weight part ratio, adding the weighed regenerated polypropylene, dicumyl peroxide, polyethylene glycol-4-cyano-4- (phenylcarbonylthio thio) valerate, polyethylene glycol diacrylate and ethylene bis stearamide into a high-speed mixer, stirring and mixing for 20min to obtain a mixture A;
(3) adding the mixture A into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the pre-melting temperature zone is 155 ℃, the first zone is 180 ℃, the second zone is 200 ℃, the third zone is 210 ℃, the fourth zone is 200 ℃, and the discharge port temperature zone is 190 ℃; the rotating speed of the screw is 300r/min, and the regenerated polypropylene material is finally prepared after melt blending, extrusion, cooling and granulation.
Comparative example 3
The comparative example provides a formula of a regenerated polypropylene material and a preparation method thereof, and the specific contents are as follows:
the raw material formula comprises the following raw materials in parts by weight:
85 parts of regenerated polypropylene, 0.005 part of free radical initiator (dicumyl peroxide), 0.05 part of free radical control agent (polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate), 0.5 part of chain extender (polyethylene glycol diacrylate), 8 parts of flexibilizer (ethylene propylene diene monomer grafted maleic anhydride copolymer), 6 parts of reinforcing agent (calcium carbonate) and 0.4 part of processing aid (ethylene bis stearamide);
the preparation method comprises the following steps:
(1) drying the regenerated polypropylene at the temperature of 70 ℃ for 3 h;
(2) according to the weight part ratio, adding the weighed regenerated polypropylene, dicumyl peroxide, polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate, polyethylene glycol diacrylate, ethylene propylene diene monomer grafted maleic anhydride copolymer, calcium carbonate and ethylene bis stearamide into a high-speed mixer, and stirring and mixing for 20min to obtain a mixture A;
(3) adding the mixture A into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the pre-melting temperature zone is 155 ℃, the first zone is 180 ℃, the second zone is 200 ℃, the third zone is 210 ℃, the fourth zone is 200 ℃, and the discharge port temperature zone is 190 ℃; the rotating speed of the screw is 300r/min, and the heat-resistant regenerated polypropylene material is finally prepared after melt blending, extrusion, cooling and granulation treatment.
Comparative example 4
The comparative example provides a formula of a regenerated polypropylene material and a preparation method thereof, and the specific contents are as follows:
the raw material formula comprises the following raw materials in parts by weight:
85 parts of regenerated polypropylene, 0.01 part of a free radical initiator (dicumyl peroxide), 0.005 part of a free radical control agent (polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate), 0.5 part of a chain extender (polyethylene glycol diacrylate), 8 parts of a flexibilizer (ethylene propylene diene monomer grafted maleic anhydride copolymer), 6 parts of a reinforcing agent (calcium carbonate) and 0.4 part of a processing aid (ethylene bis stearamide);
the preparation method comprises the following steps:
(1) drying the regenerated polypropylene at the temperature of 70 ℃ for 3 h;
(2) according to the weight part ratio, adding the weighed regenerated polypropylene, dicumyl peroxide, polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate, polyethylene glycol diacrylate, ethylene propylene diene monomer grafted maleic anhydride copolymer, calcium carbonate and ethylene bis stearamide into a high-speed mixer, and stirring and mixing for 20min to obtain a mixture A;
(3) adding the mixture A into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the pre-melting temperature zone is 155 ℃, the first zone is 180 ℃, the second zone is 200 ℃, the third zone is 210 ℃, the fourth zone is 200 ℃, and the discharge port temperature zone is 190 ℃; the rotating speed of the screw is 300r/min, and the heat-resistant regenerated polypropylene material is finally prepared after melt blending, extrusion, cooling and granulation treatment.
Comparative example 5
The comparative example provides a formula of a regenerated polypropylene material and a preparation method thereof, and the specific contents are as follows:
the raw material formula comprises the following raw materials in parts by weight:
85 parts of regenerated polypropylene, 0.01 part of a free radical initiator (dicumyl peroxide), 0.05 part of a free radical control agent (polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate), 0.1 part of a chain extender (polyethylene glycol diacrylate), 8 parts of a flexibilizer (ethylene propylene diene monomer grafted maleic anhydride copolymer), 6 parts of a reinforcing agent (calcium carbonate) and 0.4 part of a processing aid (ethylene bis stearamide);
the preparation method comprises the following steps:
(1) drying the regenerated polypropylene at the temperature of 70 ℃ for 3 h;
(2) according to the weight part ratio, adding the weighed regenerated polypropylene, dicumyl peroxide, polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate, polyethylene glycol diacrylate, ethylene propylene diene monomer grafted maleic anhydride copolymer, calcium carbonate and ethylene bis stearamide into a high-speed mixer, and stirring and mixing for 20min to obtain a mixture A;
(3) adding the mixture A into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the pre-melting temperature zone is 155 ℃, the first zone is 180 ℃, the second zone is 200 ℃, the third zone is 210 ℃, the fourth zone is 200 ℃, and the discharge port temperature zone is 190 ℃; the rotating speed of the screw is 300r/min, and the heat-resistant regenerated polypropylene material is finally prepared after melt blending, extrusion, cooling and granulation treatment.
Example 1
The embodiment provides a formula of a regenerated polypropylene material and a preparation method thereof, and the specific contents are as follows:
the raw material formula comprises the following raw materials in parts by weight:
85 parts of regenerated polypropylene, 0.01 part of a free radical initiator (dicumyl peroxide), 0.1 part of a free radical control agent (polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate), 0.5 part of a chain extender (polyethylene glycol diacrylate), 8 parts of a flexibilizer (ethylene propylene diene monomer grafted maleic anhydride copolymer), 6 parts of a reinforcing agent (calcium carbonate) and 0.4 part of a processing aid (ethylene bis stearamide);
the preparation method comprises the following steps:
(1) drying the regenerated polypropylene at the temperature of 70 ℃ for 3 h;
(2) according to the weight part ratio, adding the weighed regenerated polypropylene, dicumyl peroxide, polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate, polyethylene glycol diacrylate, ethylene propylene diene monomer grafted maleic anhydride copolymer, calcium carbonate and ethylene bis stearamide into a high-speed mixer, and stirring and mixing for 20min to obtain a mixture A;
(3) adding the mixture A into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the pre-melting temperature zone is 155 ℃, the first zone is 180 ℃, the second zone is 200 ℃, the third zone is 210 ℃, the fourth zone is 200 ℃, and the discharge port temperature zone is 190 ℃; the rotating speed of the screw is 300r/min, and the heat-resistant regenerated polypropylene material is finally prepared after melt blending, extrusion, cooling and granulation treatment.
Example 2
The embodiment provides a formula of a regenerated polypropylene material and a preparation method thereof, and the specific contents are as follows:
the raw material formula comprises the following raw materials in parts by weight:
85 parts of regenerated polypropylene, 0.05 part of a free radical initiator (dicumyl peroxide), 0.5 part of a free radical control agent (polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate), 2 parts of a chain extender (1, 6-hexanediol ethoxy acid diacrylate), 6 parts of a flexibilizer (ethylene propylene diene monomer grafted maleic anhydride copolymer), and 6 parts of a reinforcing agent (calcium carbonate) and 0.4 part of a processing aid (ethylene bis stearamide);
the preparation method comprises the following steps:
(1) drying the regenerated polypropylene at the temperature of 70 ℃ for 2 h;
(2) according to the weight part ratio, adding the weighed regenerated polypropylene, dicumyl peroxide, polyethylene glycol-4-cyano-4- (phenylcarbonylthio thio) valerate, 1, 6-hexanediol ethoxy acid diacrylate, ethylene propylene diene monomer grafted maleic anhydride copolymer, calcium carbonate and ethylene bis stearamide into a high-speed mixer, and stirring and mixing for 25min to obtain a mixture A;
(3) adding the mixture A into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the pre-melting temperature zone is 160 ℃, the first zone is 190 ℃, the second zone is 210 ℃, the third zone is 220 ℃, the fourth zone is 210 ℃ and the discharge port is 200 ℃; the rotating speed of the screw is 360r/min, and the heat-resistant regenerated polypropylene material is finally prepared after melt blending, extrusion, cooling and granulation treatment.
Example 3
The embodiment provides a formula of a regenerated polypropylene material and a preparation method thereof, and the specific contents are as follows:
the raw material formula comprises the following raw materials in parts by weight:
85 parts of regenerated polypropylene, 0.01 part of a free radical initiator (tert-butyl peroxybenzoate), 0.1 part of a free radical control agent (polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate), 2 parts of a chain extender (polyethylene glycol diacrylate), 6 parts of a flexibilizer (ethylene propylene diene monomer grafted maleic anhydride copolymer), 6 parts of a reinforcing agent (calcium carbonate) and 0.4 part of a processing aid (ethylene bis stearamide);
the preparation process comprises the following steps:
(1) drying the regenerated polypropylene at the temperature of 70 ℃ for 2 h;
(2) according to the weight part ratio, adding the weighed regenerated polypropylene, tert-butyl peroxybenzoate, polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate, polyethylene glycol diacrylate, ethylene propylene diene monomer grafted maleic anhydride copolymer, calcium carbonate and ethylene bis stearamide into a high-speed mixer, and stirring and mixing for 25min to obtain a mixture A;
(3) adding the mixture A into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the pre-melting temperature zone is 160 ℃, the first zone is 190 ℃, the second zone is 210 ℃, the third zone is 220 ℃, the fourth zone is 210 ℃ and the discharge port is 200 ℃; the rotating speed of the screw is 300r/min, and the heat-resistant regenerated polypropylene material is finally prepared after melt blending, extrusion, cooling and granulation treatment.
Example 4
The embodiment provides a formula of a regenerated polypropylene material and a preparation method thereof, and the specific contents are as follows:
the raw material formula comprises the following raw materials in parts by weight:
85 parts of regenerated polypropylene, 0.01 part of a free radical initiator (tert-butyl peroxymaleate), 0.1 part of a free radical control agent (polyethylene glycol-4-cyano-4- (phenylcarbonylthiothio) valerate), 2 parts of a chain extender (polyethylene glycol diacrylate), 6 parts of a toughening agent (ethylene propylene diene monomer grafted maleic anhydride copolymer), 6 parts of a reinforcing agent (calcium carbonate) and 0.4 part of a processing aid (ethylene bis stearamide);
the preparation method comprises the following steps:
(1) drying the regenerated polypropylene at the temperature of 70 ℃ for 2 h;
(2) according to the weight part ratio, adding the weighed regenerated polypropylene, tert-butyl peroxymaleate, polyethylene glycol-4-cyano-4- (phenylcarbonylthio thio) valerate, polyethylene glycol diacrylate, ethylene propylene diene monomer grafted maleic anhydride copolymer, calcium carbonate and ethylene bis stearamide into a high-speed mixer, and stirring and mixing for 25min to obtain a mixture A;
(3) adding the mixture A into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the pre-melting temperature zone is 160 ℃, the first zone is 190 ℃, the second zone is 210 ℃, the third zone is 220 ℃, the fourth zone is 210 ℃ and the discharge port is 200 ℃; the rotating speed of the screw is 300r/min, and the heat-resistant regenerated polypropylene material is finally prepared after melt blending, extrusion, cooling and granulation treatment.
Example 5
The embodiment provides a formula of a regenerated polypropylene material and a preparation method thereof, and the specific contents are as follows:
the raw material formula comprises the following raw materials in parts by weight:
85 parts of regenerated polypropylene, 0.05 part of a free radical initiator (tert-butyl cumyl peroxide), 0.5 part of a free radical control agent (benzyl benzodithiocarbamate), 2 parts of a chain extender (1, 6-hexanediol ethoxy acid diacrylate), 6 parts of a toughening agent (ethylene propylene diene monomer grafted maleic anhydride copolymer), 6 parts of a reinforcing agent (calcium carbonate) and 0.4 part of a processing aid (ethylene bis stearamide);
the preparation process comprises the following steps:
(1) drying the regenerated polypropylene at the temperature of 70 ℃ for 3 h;
(2) according to the weight part ratio, adding the weighed regenerated polypropylene, tert-butyl cumyl peroxide, benzyl benzodithiocarbamate, 1, 6-hexanediol ethoxy acid diacrylate, ethylene propylene diene monomer grafted maleic anhydride copolymer, calcium carbonate and ethylene bis stearamide into a high-speed mixer, and stirring and mixing for 25min to obtain a mixture A;
(3) adding the mixture A into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: the pre-melting temperature zone is 160 ℃, the first zone is 190 ℃, the second zone is 210 ℃, the third zone is 220 ℃, the fourth zone is 210 ℃ and the discharge port is 200 ℃; the rotating speed of the screw is 350r/min, and the heat-resistant regenerated polypropylene material is finally prepared after melt blending, extrusion, cooling and granulation treatment.
Example 6
The embodiment provides a formula of a regenerated polypropylene material and a preparation method thereof, and the specific contents are as follows:
the raw material formula comprises the following raw materials in parts by weight:
90 parts of regenerated polypropylene, 0.02 part of free radical initiator (dicumyl peroxide), 0.2 part of free radical control agent (benzyl benzodithiocarbamate), 1.0 part of chain extender (polyethylene glycol diacrylate), 4 parts of flexibilizer (ethylene propylene diene monomer grafted maleic anhydride copolymer), 5 parts of reinforcing agent (calcium carbonate) and 0.4 part of processing aid (ethylene bis stearamide);
the preparation process comprises the following steps:
(1) drying the regenerated polypropylene at the temperature of 70 ℃ for 3 h;
(2) adding the weighed regenerated polypropylene, dicumyl peroxide, benzyl benzodithiocarbamate, polyethylene glycol diacrylate, ethylene propylene diene monomer grafted maleic anhydride copolymer, calcium carbonate and ethylene bis stearamide into a high-speed mixer according to the mass part ratio, and stirring and mixing for 20min to obtain a mixture A;
(3) adding the mixture A into a double-screw extruder, wherein the temperature of the double-screw extruder is set as follows: 155 ℃, 180 ℃ in the first area, 200 ℃ in the second area, 210 ℃ in the third area, 200 ℃ in the fourth area and 190 ℃ in the temperature area of a discharge hole; the rotating speed of the screw is 350r/min, and the heat-resistant regenerated polypropylene material is finally prepared after melt blending, extrusion, cooling and granulation treatment.
And (3) performance testing:
the recycled polypropylene materials prepared in the above examples and comparative examples were tested for tensile strength, elongation at break, impact strength, vicat softening temperature, etc., and the results of the tests are shown in the following table:
TABLE 1 recycled Polypropylene Material Performance test results statistics
As can be seen from the above table, the heat-resistant recycled polypropylene materials of examples 1 to 6 have tensile strength of not less than 30MPa, elongation at break of up to 66%, and IZOD impact strength of up to 20.6KJ/m2Wei (vitamin)The softening temperature of the resin is more than or equal to 90 ℃, and the resin is obviously superior to the regenerated polypropylene material in the aspects of tensile strength, elongation at break, IZOD impact strength, Vicat softening temperature and the like, thereby showing that the invention realizes the generation of in-situ block/graft polypropylene by adding a free radical initiator and a free radical control agent in the preparation process and by virtue of the controllability of reversible addition-fragmentation chain transfer polymerization, can improve the mechanical property and heat resistance of the regenerated polypropylene matrix, and can further enhance the toughened regenerated polypropylene by combining a toughening agent and a reinforcing agent on the basis so as to meet the use requirements of parts such as refrigerator evaporating dishes and the like.